Dimerized fatty acid based polyamides useful for clear candle and gel applications

ABSTRACT

Blooming and/or syneresis in gel formulations can be reduced or eliminated by adding to an organic mixture an effective amount of a polyamide gelling agent having a softening point of less than about 105° C. wherein the polyamide is the reaction product of one or more diamines, optionally one or more mono-amines, one or more hydrogenated C36 dimer acids, optionally one or more C 2-22  dicarboxylic acids, and optionally one or more C 2-22  monocarboxylic acids.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of copending provisionalapplication Ser. No. 60/211,833, filed on Jun. 15, 2000, the entirecontents of which are incorporated herein by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0002] Not Applicable.

BACKGROUND THE INVENTION

[0003] Polyamide gelling agents for use in transparent gel formulationssuch as transparent candles and personal care products such as cleardeodorant gels have caused products into which they are added to exhibitblooming and syneresis. Known clear candle compositions utilizingcommercially available polyamide resins such as VERSAMID® 940 orVERSAMID® 1655 as a gelling resin demonstrated poor long-term resistanceto blooming and syneresis. Similar problems have occurred with clear gelpersonal products containing polyamide gelling agents and are describedin U.S. Pat. No. 5,500,209, the Background of the Invention section ofwhich is incorporated herein by reference.

SUMMARY OF THE INVENTION

[0004] The present invention pertains to a method for reducing oreliminating blooming and/or syneresis in a gel formulation comprisingadding to an organic mixture an effective amount of a polyamide gellingagent having a softening point of less than about 105° C. wherein thepolyamide is the reaction product of one or more diamines, optionallyone or more mono-amines, one or more hydrogenated C36 dimer acids,optionally one or more C2-22 dicarboxylic acids, and optionally one ormore C2-22 monocarboxylic acids.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

[0005] None

DETAILED DESCRIPTION OF THE INVENTION

[0006] The term “gel” as used herein is defined in Almdale et al.(Polymer Gels and Networks, Vol. 1, No. 5 (1993)) according to thefollowing two criteria: (1) a substance that consists of two or morecomponents, one of which is a liquid, present in substantial quantities;and (2) a gel is a soft material which is solid or solid-like. A gel canalso be defined according to its rheological properties. Thus, the term“gel” applies to systems having a value G′(w) that is higher than itsvalue of G″(w) at low frequencies. G′(w) is the storage modulus whichexhibits a pronounced plateau at higher frequencies (on the order of1-100 radians/second), and G″(w) is the loss modulus which isconsiderably smaller than the storage modulus in the plateau region. Agel is free-standing or self-supporting in that its yield value isgreater than the sheer stress imposed by gravity.

[0007] The diamines that can be used to make the polyamides according tothe invention are comprised of two or more aliphatic or cycloaliphatic,linear or branched, saturated or unsaturated diamines which whencopolymerized with the acid moieties described herein will produce apolyamide resin having a softening point of less than about 105° C.Examples of the diamines that can be present in the diamine mixtureinclude, but are not limited to, ethylene diamine, 1,2- and1,3-propylene diamine, teramethylene diamine, hexamethylene diamine,octamethylene diamine, 1,2-diaminocyclohexane,1,3-bis(aminomethyl)cyclohexane and combinations thereof. The diaminesalso include polyether diamines which can be poly(ethylene oxide)α,ω-diamine or poly(propylene oxide) α,ω-diamine orpoly(ethylene-co-propylene oxide) α,ω-diamine of various molecularweights and as well poly(ethylene oxide) or poly(propylene oxide)monoamines and triamines. Polyether amines are commercially availableas, for example, JEFFAMINE®™ polyether diamines, available from HuntsmanChemical.

[0008] The monoamines that can be used to make the polyamides accordingto the invention include any aliphatic or alicyclic, saturated orunsaturated, linear or branched chain monoamine having from C₂ to C₆₀carbon atoms. Polyether monoamines are also included and arecommercially available as, for example, JEFFAMINE®™ polyethermonoamines, available from Huntsman Chemical.

[0009] The hydrogenated dimer acids are those made by polymerizingunsaturated mono- and polyunsaturated fatty acids or a mixture thereof.Such acids can be made by the processes described in U.S. Pat. Nos.2,955,121; 3,412,039; and 3,507,890, the entire contents of each ofwhich is incorporated herein by reference. Such dimer acids arecommercially available as, for example, EMPOL® 1008, EMPOL® 1004, EMPOL®1025, EMPOL® 1011, or EMPOL® 1062 dimer acid from Cognis Corporation,Cincinnati, Ohio.

[0010] The C₂₋₂₂ dicarboxylic acids can be one or a mixture ofdicarboxylic acids having from 2 to 22 carbon atoms examples of whichinclude, but are not limited to malonic acid, succinic acid, adipicacid, azelaic acid, dodecanedioc acid and octadecenedioc acid.

[0011] The C₂₋₂₂ monocarboxylic acids can be any aliphatic, saturated orunsaturated, linear or branched monocarboxylic acid having from 2 to 22carbon atoms. Examples of such acids include, but are not limited to,capryic acid, lauric acid, palmitic acid, palmitoleic acid, oleic acid,linoleic acid, isostearic acid, arachidic acid and arachidonic acid.

[0012] A preferred polyamide resin is the reaction product of ahydrogenated dimer acid, stearic acid, azelaic acid, ethylene diamine,and a polypropyleneoxide diamine having a mole. Wt. of about 230.Another preferred polyamide resin is the reaction product of ahydrogenated dimer acid, stearic acid, azelaic acid, ethylene diamine,and hexamethylene diamine.

[0013] Candle formulations containing polyamide resin gelling agentsaccording to the invention exhibit better color stability in the meltand better compatibility with other ingredients than standard candleformulations. These lower softening point resins allow for formulatedgels that can melt and wick at lower temperatures resulting in lessthermal degradation and less discoloration of the melt. Also, highersoftening point resin result in formulated gels with higher meltingpoints which can approach the flash point of the fragrance or other gelingredients and cause flaring of the whole candle surface. While thesoftening point of the polyamide resins according to the invention areless than about 105° C., they are preferably between 65° C. to 95° C.,even more preferable between 75° C. to 90° C. have unexpectedly beenfound to provide better compatibility and less syneresis and blooming.

[0014] The polyamide resins according to the invention can also be usedin such products as air-freshener gels where the polyamide is used togel a fragrance composition, but not for burning. Polyamides are knownto have desirable fragrance release and can be used in air-freshenerswhere the material, unlike candles, do not require heat to release thefragrance. Such gels are known to release their desired fragrance morereadily. Other uses of the polyamide resins according to the inventioninclude gelling agents for personal care and cosmetics applications suchas deodorant gels and lipstick respectively.

[0015] The polyamide resins according to the invention can also be usedin personal care products, e.g., cosmetics such as eye make-up,lipstick, foundation make-up, costume make-up, as well as baby oil,make-up removers, bath oil, skin moisturizers, sun care products, lipbalm, waterless hand cleaner, medicated ointments, ethnic hair careproducts, perfume, cologne, and suppositories. Formulations to preparesuch materials are well known in the art. For example, U.S. Pat. Nos.3,615,289 and 3,645,705 describe the formulation of candles. U.S. Pat.Nos. 3,148,125 and 5,538,718 describe the formulation of lipstick andother cosmetic sticks. U.S. Pat. Nos. 4,275,054, 4,937,069, 5,069,897,5,102,656 and 5,500,209 each describe the formulation of deodorantand/or antiperspirant. Each of these U.S. Patents is hereby incorporatedfully herein by reference.

[0016] The method according to the invention comprises the addition of apolyamide resin gelling agent to an organic mixture. The resultingmixture is a gel. The organic mixture is any combination of organiccompounds that when mixed with a gelling agent form a gel. Suchcompounds include, for example, fatty alcohols and fatty acid estersincluding naturally occurring oils such as castor oil, peanut oil,safflower oil, sunflower oil, corn oil or cod liver oil and syntheticesters of mono and difunctional alcohols and fatty acids.

[0017] The amount of polyamide resin gelling agent that can be used inthe process according to the invention is an effective amount which isany amount that will eliminate or reduce the amount of blooming and/orsyneresis in the gel formed as a result of mixing the polyamide gellingagent and the organic resin. The effective amount will be readilyascertainable by one of ordinary skill in the art. Typically, the amountwill be in the range of from about 10% by weight of the formulation toabout 90% by weight of the formulation and preferably from about 25% byweight of the formulation to about 60% by weight of the formulation.

[0018] The following examples are meant to illustrate but not to limitthe invention. Amounts are expressed as weight percent.

[0019] In examples 1-7 below, the organic acids and 0.005% H₃PO₄catalyst were charged to a 1 liter resin kettle and heated to 180° F.under vacuum for 0.5 hour. Vacuum was broken under nitrogen, and theamines were added over 15 minutes, typically displaying a 200 to 30° C.exotherm. The mixture was heated to 440° F. over 2 hours under nitrogensweep with stirring. The reaction was held at 440° F. for 1.5 hoursafter which vacuum (15 mm Hg) was applied. The reaction was held at 440°F. for 2 hours under vacuum. Vacuum was released under nitrogen and themolten resin was cooled to 390° F. before discharging onto a Teflonsheet.

EXAMPLE 1

[0020] 81% EMPOL® 1062 hydrogenated dimer acid, 1.9% triple pressstearic acid, 0.8% azelaic acid, 5.8% ethylene diamine, and 10.5%JEFFAMINE® D230 (polypropyleneoxide diamine having a mole. Wt. of about230) were reacted at 440° F. for 1 hour under nitrogen flow and 3 hoursat 440° F. under vacuum of 15 mm Hg. Ball & Ring Softening Point 96° C.Brookfield Viscosity (@ 160° C.) 14 poise Acid value 13.0 Amine value0.3

EXAMPLE 2

[0021] 69.6% EMPOL® 1062 hydrogenated dimer acid, 11.3% triple pressstearic acid, 0.4% azelaic acid, 2.6% ethylene diamine, and 16.2%hexamethylene diamine (70% aqueous) were reacted at 440° F. for 1 hourunder nitrogen flow and 3 hours at 440° F. under vacuum of 15 mm Hg.Ball & Ring Softening Point 88° C. Brookfield Viscosity (@ 160° C.) 6.5poise Acid value 8.6 Amine value 0.4

EXAMPLE 3

[0022] 72.1% EMPOL® 1062 hydrogenated dimer acid, 11.3% isostearic acid,0.4% azelaic acid, 2.4% ethylene diamine, and 13.8% hexamethylenediamine (70% aqueous) were reacted at 440° F. for 1 hour under nitrogenflow and 3 hours at 440° F. under vacuum of 15 mm Hg. Ball & RingSoftening Point 89° C. Brookfield Viscosity (@ 160° C.) 6.0 poise Acidvalue 6.1 Amine value 0.2

EXAMPLE 4

[0023] 70.2% EMPOL® 1062 hydrogenated dimer acid, 11.3% triple pressstearic acid, 0.4% azelaic acid, 3.8% ethylene diamine, 10.3%hexamethylene diamine (70% aqueous), and 4.0% JEFFAMINE® D230 (polyetherdiamine from Huntsman Chemical) were reacted at 440° F. for 1 hour undernitrogen flow and 3 hours at 440° F. under vacuum of 15 mm Hg. Ball &Ring Softening Point 92° C. Brookfield Viscosity (@ 160° C.) 4.0 poiseAcid value 4.0 Amine value 1.5

EXAMPLE 5

[0024] 34.15% EMPOL® 1062 hydrogenated dimer acid, 15.56% triple pressstearic acid, 33.84% isostearic acid, and 16.46% 1,2-diaminocyclohexane(mixture of cis and trans) were reacted at 440° F. for 1 hour undernitrogen flow and 3 hours at 440° F. under vacuum of 15 mm Hg. Ball &Ring Softening Point 105° C. Brookfield Viscosity (@ 160° C.) 0.5 poise

EXAMPLE 6

[0025] 38.0% EMPOL® 1062 hydrogenated dimer acid, 19.2% triple pressstearic acid, 25.1% isostearic acid, 1.9% ethylene diamine, and 15.8% of1,3-bis(aminomethyl)cyclohexane were reacted at 440° F. for 1 hour undernitrogen flow and 3 hours at 440° F. under vacuum of 15 mm Hg. Ball &Ring Softening Point 99° C. Brookfield Viscosity (@ 160° C.) 0.8 poise

EXAMPLE 7

[0026] 71.6% EMPOL® 1062 hydrogenated dimer acid, 4.7% ethylene diamine,19.6% JEFFAMINE® XTJ505 and 4.2% hexamethylene diamine (70% aqueous)were reacted at 440° F. for 1 hour under nitrogen flow and 3 hours at440° F. under vacuum of 15 mm Hg.

[0027] In examples 8-19 below, the compositions were prepared bycombining the resin and both dry and liquid ingredients in a 100 mlflask and heating to 100° C. under a nitrogen blanket while stirringwith a magnetic stir bar. Once homogeneous, the resin solutions werepoured in aluminum dishes and allowed to cool.

[0028] Gel Ingredients:

[0029] 90/95 HD-oleyl alcohol is a product of Cognis Corporation.

[0030] GUERBITOL® 20 is isoarachidyl alcohol, a product of CognisCorporation.

[0031] GUERBITOL® 16 is isocetyl alcohol, a product of CognisCorporation.

[0032] EMERY® 3389 is isostearyl alcohol, a product of CognisCorporation.

[0033] SPEZIOL® 1070 is a hydrogenated C36 dimer diol, a product ofCognis Corporation.

[0034] SPEZIOL® 1075 is a C36 dimer diol, a product of CognisCorporation.

[0035] EMPOL® 1008 is a C36 diacid, a product of Cognis Corporation.

[0036] TEXAPRINT SSEH is a fatty acid ester, a product of CognisDeutschland GmbH.

[0037] TEXAPRINT SKEH is a fatty acid ester, a product of CognisDeutschland GmbH.

[0038] EDENOL® 9058 is 2-ethylhexyl azelate, a product of CognisCorporation.

[0039] EMEREST® 2326 is a butyl stearate, a product of CognisCorporation.

[0040] EMERY® 2218 is a methyl stearate, a product of CognisCorporation.

[0041] EMEREST® 2384 is a propylene glycol isostearate, a product ofCognis Corporation.

[0042] EMEREST® 2712 is a PEG-8 distearate, a product of CognisCorporation.

[0043] PARACIN 220 is the N-(2-hydroxyethyl)-12-hydroxystearamide, aproduct of Caschem.

[0044] AMIDOX L5 is an ethoxylated lauric acid amide, a product ofStepan.

[0045] EMSORB® 2500 is a sorbitan monooleate, a product of CognisCorporation.

[0046] EMSORB® 2503 is a sorbitan trioleate, a product of CognisCorporation.

[0047] STANDAMID® KD is a cocamide-diethanol amine adduct, a product ofCognis Corporation.

EXAMPLE 8

[0048] 14 g Resin from Example #1

[0049] 14 g TEXAPRINT SSEH

[0050] 14 g 90/95 HD-oleyl alcohol

[0051] 6 g EMEREST® 2384

[0052] The mixture formed a stable, soft, clear gel which showed noblooming or syneresis.

EXAMPLE 9 COMPARATIVE EXAMPLE

[0053] 14 g VERSAMID® 1655

[0054] 14 g TEXAPRINT SSEH

[0055] 14 g 90/95 HD-oleyl alcohol

[0056] 6 g EMEREST® 2384

[0057] The mixture formed a slightly hazy gel which exhibited decreasingclarity over time and suffered from syneresis of liquids to the surface.

EXAMPLE 10

[0058] 48 g Example #8

[0059] 2 g EMERY® 2218 methylstearate

[0060] The blend resulted in a gel similar to the composition in Example#8 except with a higher melting point and a harder, less elastic gel.

EXAMPLE 11

[0061] 48 g Example #8

[0062] 2 g EMEREST® 2712

[0063] The blend resulted in a gel similar to the composition in Example#8 except with a higher melting point, a harder, less elastic gel and avery slight haziness.

EXAMPLE 12

[0064] 45 g Resin from Example #4

[0065] 20 g TEXAPRINT SSEH

[0066] 15 g 90/95 HD-oleyl alcohol

[0067] 10 g EMEREST® 2384

[0068] 5 g AMIDOX L5

[0069] The mixture formed a stable, clear gel which did not exhibitsyneresis or blooming.

EXAMPLE 13

[0070] 50 g Resin from Example #4

[0071] 10 g TEXAPRINT SSEH

[0072] 25 g 90/95 HD-oleyl alcohol

[0073] 15 g EMEREST® 2384

[0074] 2 g EMSORB® 2500 Sorbitan monooleate

[0075] The mixture formed a stable, clear gel which did not exhibitsyneresis or blooming.

EXAMPLE 14

[0076] 50 g Resin from Example #4

[0077] 20 g TEXAPRINT SSEH

[0078] 15 g 90/95 HD-oleyl alcohol

[0079] 15 g EMEREST® 2384

[0080] 2 g EMSORB® 2500 Sorbitan monooleate

[0081] The mixture formed a stable, clear gel which did not exhibitsyneresis or blooming and was harder than the gel in Example #13.

EXAMPLE 15

[0082] 35 g Resin from Example #2

[0083] 38 g TEXAPRINT SSEH

[0084] 12 g 90/95 HD-oleyl alcohol

[0085] 12 g EMPOL® 1008

[0086] 1 g EMSORB® 2500 Sorbitan monooleate

[0087] The mixture formed a stable, clear soft gel.

EXAMPLE 16

[0088] 35 g Resin from Example #2

[0089] 38 g TEXAPRINT SSEH

[0090] 24 g SPEZIOL® 1070

[0091] 1 g EMSORB® 2500 Sorbitan monooleate

[0092] The mixture formed a stable, clear soft gel.

EXAMPLE 17

[0093] 35 g Resin from Example #4

[0094] 38 g TEXAPRINT SSEH

[0095] 12 g SPEZIOL® 1070

[0096] 12 g EMPOL® 1008

[0097] 1 g EMSORB® 2500 Sorbitan monooleate

[0098] The mixture formed a stable, clear soft gel.

EXAMPLE 18

[0099] 35 g Resin from Example #1

[0100] 38 g TEXAPRINT SSEH

[0101] 12 g GUERBITOL® 20

[0102] 12 g EMPOL® 1008

[0103] 0.5 g Azelaic acid

[0104] 1 g EMSORB® 2500 Sorbitan monooleate

[0105] 1 g EMSORB® 2503 Sorbitan monooleate

[0106] The mixture formed a stable, clear soft gel.

EXAMPLE 19

[0107] 35 g Resin from Example #2

[0108] 8 g TEXAPRINT SSEH

[0109] 16 g SPEZIOL® 1075

[0110] 10 g PARACIN 220

[0111] 3 g AMIDOX L5

[0112] The mixture formed a stable, clear hard gel.

What is claimed is:
 1. A method for reducing or eliminating bloomingand/or syneresis in a gel formulation comprising adding to an organicmixture an effective amount of a polyamide gelling agent having asoftening point of less than about 105° C. wherein the polyamide is thereaction product of one or more diamines, optionally one or moremono-amines, one or more hydrogenated C36 dimer acids, optionally one ormore C₂₋₂₂ dicarboxylic acids, and optionally one or more C₂₋₂₂monocarboxylic acids.
 2. The method of claim 1 wherein the dicarboxylicacid is azelaic acid.
 3. The method of claim 1 wherein the diamine isethylene diamine.
 4. The method of claim 1 wherein the diamine mixtureis comprised of ethylene diamine and a polyether diamine.
 5. The methodof claim 1 wherein the diamine mixture is comprised of ethylene diamineand a hexamethylene diamine.
 6. The method of claim 1 wherein theeffective amount is from about 10% by weight to about 90% by weight ofthe formulation.
 7. The method of claim 1 wherein the effective amountis from about 25% by weight to about 60% by weight of the formulation.8. A method for reducing or eliminating blooming and/or syneresis in agel formulation comprising adding to an organic mixture an effectiveamount of a polyamide gelling agent having a softening point of lessthan about 105° C. wherein the polyamide is the reaction product of ahydrogenated dimer acid, stearic acid, azelaic acid, ethylene diamine,and a polypropyleneoxide diamine having a mole. Wt. of about
 230. 9. Amethod for reducing or eliminating blooming and/or syneresis in a gelformulation comprising adding to an organic mixture an effective amountof a polyamide gelling agent having a softening point of less than about105° C. wherein the polyamide is the reaction product of a hydrogenateddimer acid, stearic acid, azelaic acid, ethylene diamine, andhexamethylene diamine.